JPS6224458B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to new anthraquinone compounds as well as mixtures thereof, processes for the preparation of these compounds, the application of these compounds as dyes for the dyeing or dyeing of natural or synthetic textile materials, and the use of these compounds for dyeing or dyeing natural or synthetic textile materials. related to textile materials. This new anthraquinone compound corresponds to the following formula in free acid form. In the formula, X is a halogen atom at the 6- or 7-position of anthraquinone, R ₁ and R ₂ are independently alkyl groups having 1 to 4 carbon atoms, and R ₃ is a hydrogen atom or a carbon atom. an alkyl group with 1 to 4 atoms, and one Z is a group -CH ₂
-NH-CO-Y, where Y is an alkyl group having 1 to 4 carbon atoms, which is unsubstituted or mono- or di-substituted by a halogen atom, or alkyl group having 2 to 4 carbon atoms. Z is a hydrogen atom or a group -CH ₂ -NH-CO- Y (where Y has the meaning given above). Preferred anthraquinone compounds are mixtures of 6-halogen-anthraquinone compounds and 7-halogen-anthraquinone compounds. X in the sense of a halogen atom is, for example, a fluorine atom, a chlorine atom or a bromine atom. In preferred anthraquinone compounds, X means a chlorine atom. R ₁ , R ₂ and R ₃ in the meaning of alkyl radicals independently of one another represent an unbranched or branched alkyl radical having 1 to 4 carbon atoms.
For example, methyl, ethyl, n- and isopropyl groups and also n-, 2- or 3-butyl groups come into consideration here. In preferred anthraquinone compounds, R ₁ , R ₂ and R ₃ each mean the same unbranched alkyl group having 1 to 4 carbon atoms, especially a CH ₃ - group. When Y in the group --CH ₂ --NH--CO--Y represents an alkyl group having 1 to 4 carbon atoms, the aforementioned groups come into question. As an alkenyl group, Y means in particular the group -CH=CH ₂ . In preferred anthraquinone compounds, one Z is a hydrogen atom and the other Z is a group -
_CH2 -NH-CO-Y (where Y represents a _-CH2Cl group or a phenyl group). Furthermore, both Z
is the group _-CH2NH -CO-Y, for example both Z are the group _-CH2 -NH-CO-CH2Cl, or one Z is the group _{CH2- NHCOCH2Cl and} the other Of interest are also anthraquinone compounds in which Z is the group CH ₂ NHCO.C ₆ H ₅ . The phenyl group Y is advantageously unsubstituted. The new anthraquinone compounds of the formula () and mixtures thereof are water-soluble, blue-coloured compounds which have good dyeing ability and good sunlight and wet fastness for textile materials, especially for polyamide materials. The new anthraquinone compounds and mixtures thereof are obtained as follows. i.e. the expression (In the formula, X and Hal are each independently a halogen atom.) (In the formula, R ₁ and R ₂ are independently an alkyl group having 1 to 4 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) and a group -CH ₂ -NH-CO-Y, where Y is an alkyl group having 1 to 4 carbon atoms, which is unsubstituted or mono- or di-substituted by a halogen atom or An alkenyl group having 2 to 4 carbon atoms or a phenyl group which is unsubstituted or mono- or di-substituted by a halogen atom) is reacted with a compound which introduces the phenyl group. The introduction of the substituent -CH ₂ -NH-CO-Y into one position Z or both positions Z of the benzene nucleus is carried out according to Tscherniak-Einhorn.
Einhorn), do the following: That is, an anthraquinone compound or a mixture of anthraquinone compounds obtained from the reaction of compound () and compound () is reacted with an N-methylolamide having a -COY group on the N-atom in an acidic medium, preferably concentrated sulfuric acid. Suitable N-methylolamides are for example N-methylolbenzamide, N-methylol-2,4-dichlorobenzamide, N-
Methylol-2-chlorobenzamide and N-
Methylol-4-chlorobenzamide. Anthraquinone compounds of formula () and phenylamines of formula () are known. For example, the following anthraquinone compounds of formula () are problematic. 1-amino-4-bromo-6-
Chlor-anthraquinone-2-sulfonic acid, 1-
Amino-4-bromo-7-chloro-anthraquinone-2-sulfonic acid and 1-amino-4-bromo-6-chloro-anthraquinone-2-sulfonic acid and 1-amino-4-bromo-7-chloro-
(1:1) mixture of anthraquinone-2-sulfonic acids. As the phenylamine of formula (), for example, 2.
4,6-trimethylaniline, 2-methyl-6-
Mention may be made of ethylaniline and 2,6-dimethylaniline. The condensation reaction of a compound of formula () with a compound of formula () can be carried out by known methods, for example in a mixture of water and an organic medium (for example cellosolve or an alcohol such as methanol or ethanol).
at a temperature of about 70-100°C, depending on the boiling point of the solvent used, and a catalyst such as copper powder or copper salts and
Perform in the presence of a base such as _NaHCO3 . Anthraquinone compounds of formula () can be made by various methods. For example, the 1,6 and/or 1,7-dihalogenanthraquinones are aminated according to the method of DE 2604830, and then the 2-position is sulfonated, for example using chlorosulfonic acid, and the 4-position is sulfonated. Obtained by halogenation, especially bromination. Another possibility to do this is as follows. Anthraquinone compounds that are monosulfonated at the 6- and/or 7-positions are nitrated at the 1-position and then monosulfonated at the 6- and/or 7-positions.
exchanging the sulfo group at the -position with a halogen, particularly a chlorine atom, reducing the nitro group at the 1-position to an amino group, and sulfonating this 1-amino-6/7-halogen-anthraquinone compound at the 2-position as directed; Then, the compound is halogenated at the 4-position to obtain an anthraquinone compound of formula (). Anthraquinone compounds of the formula () and mixtures thereof can be used in the exhaust or continuous dyeing process of natural or synthetic textile materials that can be dyed with acid dyes or fiber-reactive dyes, as well as polyamide materials such as nylon and wool, and cellulosic materials. It has particular use as a dye for dyeing by conventional methods such as dyeing or summer dyeing. These materials can then be of various types of finishes, such as fibres, threads, fabrics, textiles, accessories and ready-made products such as shirts and sweaters. The dyeings obtained on these materials are characterized by a good pure blue shade under artificial light and also by good fastness to moisture, sunlight and ozone. One advantage of the present invention is that hitherto worthless waste products, such as slurry products from the nitration of anthraquinones, can be used as raw materials for the production of the anthraquinone compounds of the present invention. The following examples illustrate the invention without limiting it thereto. Parts are given in parts by weight and temperatures in °C. The symbol 6/7-chloroanthraquinone means that a mixture of 6-chloroanthraquinone and 7-chloroanthraquinone compounds is being treated. Anthraquinone compounds can be present in the free acid form or as alkali salts such as ammonium, sodium, potassium or lithium salts. Based on the color index Hue Indication Chart as color tone data obtained on textile materials.
Hue term and Indicator No. are listed. Example 1 43.9 parts of the sodium salt of a mixture of 1-amino-4-bromo-6-chloro-anthraquinone-2-sulfonic acid and 1-amino-4-bromo-7-chloro-anthraquinone-2-sulfonic acid were added to 250 parts of water. 1 part and 20 parts of mecidine in 80 parts of methanol and 20 parts of sodium bicarbonate and knead into a slurry. The mixture is heated to 75°C and 0.6 part of copper powder is sprinkled in while stirring well. Stir at 80-85° for 15 hours to complete the reaction. Excess methidine is expelled with steam. 300 parts of methanol are added to the residue and the hot alcohol and water dye solution is separated from the copper catalyst by filtration. The filtrate is made acidic with dilute hydrochloric acid. The dye will then settle out. This is filtered with suction and washed with dilute hydrochloric acid. Add the suction filtrate to 300 parts of water to form a slurry. Then adjust the pH to 7.5 with a dilute aqueous sodium hydroxide solution, warm to 60°, and add 300 parts of a 20% aqueous sodium chloride solution. Then the expression The sodium salt of the dye is obtained. This is filtered with suction and the dye is dried. The dyes thus obtained have good fastness on wool and synthetic polyamide fibers in acetic or sulfuric dye baths.
Dye to a uniform tone of blue (Indicator No. 14). In the above example, if 20 parts of 2-methyl-6-ethylaniline or 18 parts of 2,6-dimethylaniline is used instead of 20 parts of mesidine, a similar blue (Indicator No. 14) with good staining properties is used. ) is obtained. 1-amino-4-brome-6/7 used as raw material
-Chloranthraquinone-2-sulfonic acid is
1.6/1.7-dichloroanthraquinone is reacted with ammonia in an autoclave according to the method described in German Patent No. 2604830, and the 1-amino-6/7-chloroanthraquinone formed is reacted with chlorosulfonic acid Obtained by sulfonation in dichlorobenzene and bromination at the 4-position. Example 2 29.6 parts of the sodium salt of the dye obtained in Example 1 was added to 0
Dissolved in 280 parts of 96% sulfuric acid at ~5° and N-
Mix with 9.4 parts of methylolbenzamide. Stir the mixture for 15 hours at 0-5°, then pour it onto ice and separate the dye as the sodium salt in the usual manner. The formula thus obtained The dyes have good wet fastness on wool and synthetic polyamide fibers from weakly acidic dye baths.
Dye to the tone of blue (Indicator No. 14). If 11.6 parts of N-methylol-2,4-dichlorobenzamide is used in place of N-methylolbenzamide in this condensation reaction under otherwise the same conditions, wool and polyamide can be similarly treated with a fastening color of blue (Indicator No. .14) You can obtain a dye for dyeing. Example 3 29.6 parts of the sodium salt of the dye obtained in Example 1 was added to 15
Dissolves in 280 parts of 96% sulfuric acid at ~20°. 8.2 parts of N-methylolchloroacetamide are charged into this solution and the mixture is stirred for 15 hours at a temperature of 15-20°. Then pour it over ice. The precipitated dye is filtered off with suction, the resulting suspension is carefully brought to pH 7 with sodium hydroxide solution and the dye is then precipitated out as the sodium salt with sodium chloride. Dry formula from this The dye represented by dyes wool a neutral blue (Indicator No. 14) from a slightly acidic dye bath. This wool dyeing has good wet fastness. In the above method, 1 mole of 1-amino-4-bromo-6/7-chloroanthraquinone-2-sulfonic acid and 2,4-
30.3 parts of dye obtained by condensation with 1 mole of dimethyl-6-ethylaniline or 1-amino-4
-bromo-6/7-chloroanthraquinone-2-
If 32 parts of the sodium salt of a dye obtained by condensation of 1 mole of sulfonic acid and 1 mole of 2,4,6-triethylaniline is used, wool can be dyed blue (Indicator No. 14) with good fastness. ) is obtained. Example 4 29.6 parts of the sodium salt of the dye obtained in Example 1 was added to 0
Dissolve in 280 parts of 96% sulfuric acid at ~5° and mix the solution with 6 parts of N-methylolacrylamide. Stir the mixture for 15 hours at 0-5°, then pour it onto ice and separate the dye as the sodium salt in the usual manner. The formula thus obtained The dyes have good wet fastness on wool and synthetic polyamide fibers from weakly acidic dye baths.
Dye to the tone of blue (Indicator No. 14). If 11.6 parts of N-methylol-3-chlorobenzamide is used in place of N-methylol acrylamide in this condensation reaction under otherwise the same conditions, wool and polyamide can similarly be made fast.
You can obtain dye that dyes blue (Indicator No. 14). Example 5 29.6 parts of the sodium salt of the dye obtained in Example 1 was added to 15
Dissolves in 280 parts of 96% sulfuric acid at ~20°. 16.4 parts of N-methylolchloroacetamide are charged into this solution and the mixture is stirred for 15 hours at a temperature of 15-20°. Then pour it over ice. The precipitated dye is filtered by absorption and suspended in water, the resulting suspension is carefully brought to pH 7 with sodium hydroxide solution, and the dye is then precipitated out as the sodium salt with sodium chloride. Dry formula from this The dye represented by the formula dyes wool in a neutral blue tone from a slightly acidic dyebath. This wool dyeing has good wet fastness. Reference Example A dyebath is prepared consisting of 4000 parts of water, 4 parts of ammonium acetate, 2 parts of the dye obtained in Example 1 and an amount of acetic acid such that the pH value of the dyebath is 4.5. 100 parts of synthetic polyamide tricots are charged into the dyebath thus obtained, heated to boiling within 30 minutes,
and stain for 45 minutes at 100°C. This results in a blue (Indicator No. 14) dyeing with good fastness. Comparative dyeing experiment example Structure of dye used in experiment Dye 1: Dye obtained according to Example 3 of the invention. Dye 2: This is a dye produced by a method similar to Example 4 of Japanese Patent Publication No. 37-14950, using N-methylol chloroacetamide as the methylol compound instead of N-methylol-2,4-dichlorobenzamide. Dye 3: Dye obtained according to Example 2 of the invention. Dye 4: This is a dye obtained according to Example 4 of Japanese Patent Publication No. 37-14950. Experimental Method-1 Dyeing Method In the following dyeing methods A and B, the amounts of dyes 1, 2, 3, and 4 used are different in order to obtain the same color intensity (density). Dyeing wool (dying method A) Add 1.4% (or 2.8%) of Dye 1 prepared above (4% (or 8%) when using Dye 2) and ammonium sulfate to adjust the pH value to 5-6. Liquid ratio containing 3% 1:34
A well-moistened piece of wool test material is introduced into an aqueous dyebath at 40°C. Raise the temperature of the bath to the boiling point within 45 minutes and continue dyeing at the boiling point for 60 minutes. The dyed wool pieces are then rinsed with cold water and dried. Dyeing of polyamide (Dyeing method B) 1.1% (or 2.2%) of Dye 3 prepared as above [2.2% (or 4.4%) when using Dye 4], 2 g of NaH ₂ PO ₄ per 1 and PH value of 6 A sample of polyamide material (Heranka tricots) was placed in an aqueous dyebath with a liquor ratio of 1:50 containing sufficient amounts of Na ₂ HPO ₄ to
Introduce at 40°C. Raise the temperature of the bath to the boiling point within 45 minutes and continue dyeing at the boiling point for 60 minutes. The dyed material is then rinsed with cold water and dried. -2 Fastness test (1) Dye fastness to water A sample piece of the dyed product obtained by dyeing method A was sewn together with a piece of undyed wool and a piece of undyed cotton, and then soaked in distilled water at room temperature. Soak. Excess water is poured off, then the sample is placed between two glass sheets in the test apparatus and a weight of 4.5 Kg is applied. test equipment containing the sample for 4 hours.
Warm to 37℃. Finally, the sample is removed from the test apparatus and dried in warm air. The determination results for discoloration and staining are shown in the table (below) in comparison to the gray scale. (2) Dye fastness to sweat A sample piece of the dyed product obtained by dyeing method A was sewn together with a piece of undyed wool and a piece of undyed cotton, and 5 g of sodium chloride per 1 water,
Liquid ratio 1 containing 5 g of NaH ₂ PO _{4.2H 2} O and 0.5 g of 1-histidine.HCl.H ₂ O:
Soak for 30 minutes in a solution of 50 ml. The sample was then removed from the solution, placed between two plates of a perspirometer, applied a pressure of 125 g/ ^cm2 , and
Keep at 37℃ for 4 hours. Finally, the sample is removed from the perspirometer and dried in warm air. The determination results for discoloration and staining are shown in the table (below) in comparison to the gray scale. (3) Dye fastness to hot water A sample piece of the dyed product obtained by dyeing method A is sewn together with a piece of undyed wool and a piece of undyed cotton. The sample is wound around a glass rod and treated with distilled water containing 2 mg of glacial acetic acid per water for 30 minutes at 70°C. The sample is then removed from the glass rod, squeezed, and dried in warm air. The determination results for discoloration and staining are shown in the table (below) in comparison to the gray scale. (4) Dye fastness to washing (50°C) A sample piece of the dyed product obtained by dyeing method A was sewn together with a piece of undyed wool and a piece of undyed cotton, and 5 g of soap per 1 water was added. Wash in the containing solution for 45 minutes at 50°C. The sample is then rinsed with cold water and dried. Composition of the soap used: Free alkali calculated as Na ₂ CO ₃
Free alkali calculated as up to 0.3% NaOH
Maximum 0.1% total fatty acids calculated as sodium salts
Minimum 85% Free fatty acid titer Maximum 30°C Iodide No. Maximum 50 Discoloration and staining results are compared to the gray scale and are shown in the table (below). (5) Dyeing fastness against washing (60°C) A sample piece of the dyed product obtained by dyeing method A was sewn together with a piece of undyed wool and a piece of undyed cotton, and then washed with 1 part water and 1 part soap [ For the composition of the soap used, see the section on color fastness to washing (50°C) above.
Wash for 30 minutes. The sample is then rinsed with cold water and dried. The determination results for discoloration and staining are shown in the table (below) in comparison to the gray scale. (6) Dyeing fastness against fullness The dyed sample piece obtained by dyeing method A was sewn together with an undyed wool piece and an undyed cotton piece and placed in a stainless steel sample container 50 mm in diameter.
Contains 50% soap per 1 ounce of water
Launder-Ometer containing 3 times the weight of the sample of soap solution containing 10 g of calcined sodium carbonate and 10 g of calcined sodium carbonate.
Incubate at 40°C for 2 hours. Then add enough water to bring the liquid ratio to 1:100 and continue processing at 40°C for 10 minutes. Squeeze the sample and dry in warm air. Discoloration and fading and staining are determined using an appropriate standard dye that has been subjected to the same fullening operation. Comparison with grayscale (below)
Shown in the table. Next, a sample piece of the dyed product obtained by dyeing method B is used instead of a sample piece of the dyed product obtained by dyeing method A, and the dyeing method described above is used, except that the material to be sewn with the sample piece is as follows. Repeat fastness tests (1) to (5) and number these tests as dye fastness tests (7) to (11). In dyeing fastness tests (7) (dying fastness to water), (8) (dying fastness to perspiration) and (11) [dying fastness to washing (60°C)], the dyed sample piece was stained. Sew together a piece of unstained viscose and a piece of undyed polyamide. Dye fastness test (9)
(dye fastness to hot water) and (10)
[Dyeing fastness against washing (50℃)]
In , the dyed sample piece is sewn together with a piece of undyed wool and a piece of undyed polyamide. The results of the color fastness tests (7) to (11) regarding discoloration and staining are shown in the table (below) in comparison with the gray scale.

【table】

[Table] The fastness values shown in the table and above regarding discoloration and staining are
Corresponds to the grayscale fastness values given in Schweizerische Normen-Vereinigung. (12) Affinity test Dye 3 at 2.2% (or 4.4%) [Dye 4
4.4% (or 8.8%)] to dye a sample of polyamide material using a liquid ratio of 1:25 instead of 1:50 and carrying out staining method B above completely. The exhaustion of the dyebath is determined by comparing the amount of dye in the dyebath before and after dyeing the polyamide material using a spectrophotometer (Beckmann DB-GD). The value measured by a spectrophotometer before dyeing the polyamide material is taken as 100%, and the measured value obtained after dyeing the polyamide material is shown in % in the table.

[Table] Conclusion According to each fastness grade shown in the table, dye 2
Compared to the wool dyeings with dye 1, the wool dyeings with dye 1 showed better fastness in 21 cases and equal fastness in 15 cases. According to each fastness class in the table, compared to the polyamide dyeing with dye 4, the polyamide dyeing with dye 3 shows better fastness in 16 cases, equal fastness in 10 cases,
And in four cases, the firmness was lower. In the affinity test (12), as can be seen from the values in the table, Dye 3 had better affinity for fiber materials than Dye 4. As can be drawn from the above conclusions, novel dyes 1 and 3 are superior to dyes 2 and 4 in terms of fastness to water, fastness to sweat, fastness to hot water and fastness to washing (50° C.). New dye 1 is washed (60
It is superior to Dye 2 with respect to fastness to (°C) and fastness to shrinkage. and,
New dye 3 is superior to dye 4 with respect to its affinity for polyamide fibers.

Claims (1)

[Claims] 1 formula [In the formula, X is a halogen atom at the 6- or 7-position of anthraquinone, R ₁ and R ₂ are independently alkyl groups having 1 to 4 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and one Z is a group -CH ₂
-NH-CO-Y, where Y is an alkyl group having 1 to 4 carbon atoms, which is unsubstituted or mono- or di-substituted by a halogen atom, or alkyl group having 2 to 4 carbon atoms. Z is a hydrogen atom or a group -CH ₂ -NH-CO- Y (herein, Y has the above meaning)] and mixtures thereof. 2. The anthraquinone compound according to item 1 above, which is a mixture of a 6-halogen-anthraquinone compound and a 7-halogen-anthraquinone compound of formula () according to item 1 above. 3. The preceding item 1, characterized in that X is a chlorine atom.
and 2. The anthraquinone compound according to any one of 2. 4. The preceding item 1, wherein R ₁ , R ₂ and R ₃ are each the same unbranched alkyl group.
The anthraquinone compound according to any one of 3 to 3. 5. The anthraquinone compound according to item 4, wherein each of R ₁ , R ₂ and R ₃ is a CH ₃ - group. 6 One Z is a hydrogen atom and the other Z has the formula -CH ₂ -NH-CO-Y, where Y is a group -CH ₂ Cl
or a phenyl group). 7 formula The anthraquinone compound according to the above item 1, which is represented by: 8 formula The anthraquinone compound according to the above item 1, which is represented by: 9 formula (In the formula, X and Hal are each independently a halogen atom, and X is at the 6- or 7-position of the anthraquinone.) (In the formula, R ₁ and R ₂ are independently an alkyl group having 1 to 4 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) and a group -CH ₂ -NH-CO-Y, where Y is an alkyl group having 1 to 4 carbon atoms, which is unsubstituted or mono- or di-substituted by a halogen atom or (alkenyl group having 2 to 4 carbon atoms or phenyl group which is unsubstituted or mono- or di-substituted by a halogen atom). do, expression [In the formula, X, R ₁ , R ₂ and R ₃ have the same meanings as above, and one Z is a group -CH ₂ -NH-CO-Y
(where Y has the above meaning), and the other Z is a hydrogen atom or a group -CH ₂ -NH-CO-Y (where Y has the above meaning)] and methods for preparing mixtures thereof. 10 formula [In the formula, X is a halogen atom at the 6- or 7-position of anthraquinone, R ₁ and R ₂ are independently alkyl groups having 1 to 4 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and one Z is a group -CH ₂
-NH-CO-Y, where Y is an alkyl group having 1 to 4 carbon atoms, which is unsubstituted or mono- or di-substituted by a halogen atom, or alkyl group having 2 to 4 carbon atoms. Z is a hydrogen atom or a group -CH ₂ -NH-CO- Y (wherein Y has the meaning given above)] A method for dyeing or dyeing natural or synthetic textile materials using anthraquinone compounds represented by: and mixtures thereof as dyes.